CN103420791B - The method of synthetic gas preparation of ethanol by hydrogenating - Google Patents
The method of synthetic gas preparation of ethanol by hydrogenating Download PDFInfo
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- CN103420791B CN103420791B CN201210150477.9A CN201210150477A CN103420791B CN 103420791 B CN103420791 B CN 103420791B CN 201210150477 A CN201210150477 A CN 201210150477A CN 103420791 B CN103420791 B CN 103420791B
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Abstract
The present invention relates to a kind of method of synthetic gas preparation of ethanol by hydrogenating, mainly solve in prior art and deposit in the product containing C such as acetaldehyde, ethyl acetate, acetic acid
2oxygenatedchemicals, causes the problem that ethanol selectivity is low.The present invention is comprised the following steps by employing: a) synthetic gas enter in the first reactor with the first catalyst exposure, generate containing the first plume effluent of ethanol; B) the first plume effluent enter in the second reactor with the second catalyst exposure, generate containing the reaction effluent of ethanol; Wherein, described first catalyzer is rhodium base catalyst; Described second catalyst, comprises following component: the copper of 20 ~ 80% or its oxide compound; And at least one in the iron of 20 ~ 80%, cobalt, zinc, chromium or its oxide compound; Technical scheme not containing carrier in described second catalyzer solves this problem preferably, can be used in the industrial production of synthetic gas preparation of ethanol by hydrogenating.
Description
Technical field
The present invention relates to a kind of method of synthetic gas preparation of ethanol by hydrogenating.
Background technology
Ethanol is important basic organic chemical industry raw material, is also potential liquid fuel resource.The main method of current production ethanol has the agricultural-food such as grain, sucrose fermentation method and ethylene hydration method.These two kinds of methods also exist that grain cost is high, waste residue and liquid is many, to shortcomings such as equipment corrosion are strong, development is restricted respectively.In recent years, from coal through synthetic gas (CO+H
2) prepare ethanol and day by day receive attention: on rhodium base catalyst under certain pressure and temperature condition, the C such as acetaldehyde, ethanol, ethyl acetate, acetic acid can be obtained by reacting
2oxygenatedchemicals, and these C
2acetaldehyde wherein, ethyl acetate, acetic acid hydrogenation, under the effect of catalyzer, can be changed into ethanol by oxygenatedchemicals.Sun Zhonghua is in " chemical industry and engineering " (the 31st volume the 1st phase in 2010, P9 ~ 12) describe Cu-series catalyst of butyraldehyde gas phase hydrogenation butanols and preparation method thereof in " research of butyraldehyde gas phase hydrogenation catalyzer and industrial application " literary composition, the transformation efficiency of butyraldehyde is more than 98%, and the selectivity of butanols is more than 99%.Zhao Le equality also describes the Cu-series catalyst being widely used in aldehyde hydrogenation in oxo process in " petrochemical complex " (the 33rd volume the 3rd phase in 2004, P209 ~ 211) " preparation of novel C uO/ ZnO catalyzer and the catalytic performance to aldehyde hydrogenation/alcohol dehydrogenase reaction a thereof " literary composition.Lv Zhi fruit is waited and then describe Cu-series catalyst for the reaction of hydrogenation of hydroxypentylaldehyd Hydrogenation for neopentyl glycol in " Qingdao University of Science and Technology's journal " (natural science edition) (volume the 4th phase August the 30th in 2009, P297 ~ 300) " performance of a copper-based catalysts and sign " literary composition.Zhang Yue etc. describe the reaction of Cu-series catalyst for methyl glycolate shortening preparing ethylene glycol in " chemical industry progress " (the 30th volume the 3rd phase in 2011) " methyl glycolate shortening prepares ethylene glycol " literary composition.Chen Hongmei etc. are in " gas chemical industry " (the 35th volume the 3rd phase in 2010, P1 ~ 6) then have studied the reaction of dimethyl oxalate hydrogenation synthesizing of ethylene glycol on copper-based catalysts in the research of dimethyl oxalate shortening synthesizing glycol " on the copper-based catalysts " literary composition, the transformation efficiency of dimethyl oxalate and the selectivity of ethylene glycol reach 98% and 87% respectively.The common feature of above-mentioned document is exactly different aldehydes or ester class, and all adopt Cu-series catalyst hydrogenation to generate different alcohol, this is the C such as acetaldehyde, ethyl acetate, acetic acid
2the Hydrogenation alcohol of oxygenatedchemicals provides thinking.
The open 62-59232 of document special permission describes and uses CuO/SiO
2as C such as acetaldehyde, ethyl acetate, acetic acid
2the preparing alcohol catalyst through adding hydrogen of oxygenatedchemicals.CN1230458 then adopts CuO-auxiliary agent/Al
2o
3as C
2the preparing alcohol catalyst through adding hydrogen of oxygenatedchemicals.These Cu-series catalysts are all the catalyzer of loading type.CuO/SiO
2the hydrogenation degree of catalyzer to acetic acid is lower, and CuO-auxiliary agent/Al
2o
3the bulk catalyst of catalyzer inherently synthesising gas systeming carbinol, may improve the selectivity of methyl alcohol in the reaction product, thus affect the yield of principal product ethanol.
Summary of the invention
Technical problem to be solved by this invention is deposited in prior art in the product containing C such as acetaldehyde, ethyl acetate, acetic acid
2oxygenatedchemicals, causes the problem that ethanol selectivity is low, provides a kind of method of new synthetic gas preparation of ethanol by hydrogenating.The method has the high feature of ethanol selectivity, significantly improves the yield of ethanol in synthetic gas ethanol synthesis final product.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method of synthetic gas preparation of ethanol by hydrogenating, comprises the following steps:
A) synthetic gas enter in the first reactor with the first catalyst exposure, generate containing the first plume effluent of ethanol;
B) the first plume effluent enter in the second reactor with the second catalyst exposure, generate containing the reaction effluent of ethanol;
Wherein, described first catalyzer is rhodium base catalyst; Described second catalyst, comprises following component: the copper of 20 ~ 80% or its oxide compound; And at least one in the iron of 20 ~ 80%, cobalt, zinc, chromium or its oxide compound; Not containing carrier in described second catalyzer.
In technique scheme, the first reactor reaction temperature is 290 ~ 330 DEG C, and preferable range is 305 ~ 315 DEG C; Reaction pressure is 2.0 ~ 8.0MPa, and preferable range is 3.0 ~ 5.0 MPa; Reaction volume air speed is 4500 ~ 16000 hours
-1, preferable range is 6000 ~ 12000 hours
-1.Second reactor reaction temperature is 140 ~ 250 DEG C, and preferable range is 180 ~ 220 DEG C; Reaction pressure is 2.0 ~ 8.0MPa, and preferable range is 3.0 ~ 5.0 MPa; Reaction volume air speed is 4500 ~ 16000 hours
-1, preferable range is 6000 ~ 12000 hours
-1.Described second catalyst, the consumption preferable range of copper or its oxide compound is 23 ~ 75%, and the consumption preferable range of at least one in iron, cobalt, zinc, chromium or its oxide compound is 23 ~ 75%.
The first catalyzer described in the present invention is rhodium base catalyst, and this is known in the art, such as, Rh/SiO disclosed in document Japanese Unexamined Patent Publication 62-59232
2.
The preparation method of the second catalyzer described in the present invention, comprises the following steps:
1, solution I is mixed with by being dissolved in dehydrated alcohol together with the nitrate of the iron of the cupric nitrate of aequum and aequum, cobalt, zinc or chromium or its mixture; Wherein, the weight ratio of catalyzer raw material nitrate and dehydrated alcohol is 0.15 ~ 0.40.
2, the oxalic acid of aequum is dissolved in dehydrated alcohol and is mixed with solution II; Wherein, the mol ratio of oxalic acid and catalyzer raw material nitrate is 1.1 ~ 1.4, and the weight ratio of oxalic acid and dehydrated alcohol is 0.10 ~ 0.35.
3, under the prerequisite of rapid stirring, solution I and solution II are mixed, precipitation, filter after aging 1 ~ 3 hour and obtain catalyst precursor.
4, by presoma 20 ~ 180 DEG C of dryings 1 ~ 20 hour, then in 250 ~ 550 DEG C of roastings 2 ~ 8 hours, obtain described catalyzer.
The inventive method first makes synthetic gas react on rhodium base catalyst, and obtaining acetaldehyde, ethanol, ethyl acetate and acetic acid is main C
2oxygenatedchemicals; C
2oxygenatedchemicals is again through the second catalyzer, and acetaldehyde wherein, ethyl acetate and acetic acid hydrogenation can be made ethanol by the hydrogen in unreacted synthetic gas.The second catalyzer used in the inventive method is not containing carrier, and employing copper is main catalyst component, and at least one in iron, cobalt, zinc or chromium is auxiliary agent.Because the first catalyst rhodium used in the inventive method is catalyst based for the synthesis of gas ethanol, its transformation efficiency is not high, has a large amount of material synthesis gas can enter the second reactor with the product of the first reactor; And copper-based catalysts is the custom catalysts of synthesising gas systeming carbinol, copper/zinc/aluminium oxide catalyst is its classical catalyzer, the the second catalyst reaction conditional likelihood used in reaction conditions and the inventive method, for avoiding increasing the content of methyl alcohol in final product and affecting the yield of ethanol, the second catalyzer used in the inventive method does not adopt conventional aluminum oxide as carrier.Adopt the inventive method, in final product, the selectivity of ethanol brings up to 47 ~ 54% from original 27 ~ 35%, achieves good technique effect.
Below by embodiment, the present invention is further elaborated.
Embodiment
[embodiment 1]
8 grams of cupric nitrates (containing 3 crystal water), 28.88 grams of zinc nitrates (containing 6 crystal water) are dissolved in 160 milliliters of dehydrated alcohols together; 14 grams of oxalic acid are dissolved in 80 milliliters of dehydrated alcohols, two kinds of ethanolic soln mixed precipitations under fast stirring, continue stirring 2 hours, suction filtration, filter cake drying at room temperature enters baking oven and dries 15 hours, 400 DEG C of roastings 5 hours in 110 DEG C after 2 hours, obtain CuO(25%)-ZnO(75%) catalyzer, compression molding, gets 20 ~ 40 orders stand-by, numbering JQ-1.
[embodiment 2]
15 grams of cupric nitrates (containing 3 crystal water), 17.95 grams of zinc nitrates (containing 6 crystal water), 2.5 grams of Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKESs (containing 6 crystal water) are dissolved in 155 milliliters of dehydrated alcohols together; 14.16 grams of oxalic acid are dissolved in 81 milliliters of dehydrated alcohols, two kinds of ethanolic soln mixed precipitations under fast stirring, continue stirring 2 hours, suction filtration, filter cake drying at room temperature enters baking oven and dries 15 hours, 400 DEG C of roastings 4 hours in 110 DEG C after 2 hours, obtain Cu(47.0%)-Zn(47.0%)-Co(6%) catalyzer, compression molding, gets 20 ~ 40 orders stand-by, numbering JQ-2.
[embodiment 3]
15 grams of cupric nitrates (containing 3 crystal water), 5.99 grams of zinc nitrates (containing 6 crystal water), 1.5 grams of iron nitrates (containing 9 crystal water), 1 gram of chromium nitrate (containing 9 crystal water) are dissolved in 103 milliliters of dehydrated alcohols together; 9.56 grams of oxalic acid are dissolved in 55 milliliters of dehydrated alcohols, two kinds of ethanolic soln mixed precipitations under fast stirring, continue stirring 2 hours, suction filtration, filter cake drying at room temperature enters baking oven and dries 15 hours, 400 DEG C of roastings 4 hours in 110 DEG C after 2 hours, obtain Cu(70.5%)-Zn(23.5%)-Fe(3.7%)-Cr(2.3%) catalyzer, compression molding, gets 20 ~ 40 orders stand-by, numbering JQ-3.
[comparative example 1]
Get 1/3rd of [embodiment 3] Central Plains doses (owing to adding carrier, final catalyst component content can not be identical with [embodiment 3], but the ratio of the weight percent between them is identical), be dissolved in 5 ml deionized water together by 5 grams of cupric nitrates (containing 3 crystal water), 2.0 grams of zinc nitrates (containing 6 crystal water), 0.5 gram of iron nitrate (containing 9 crystal water), 0.3 gram of chromium nitrate (containing 9 crystal water), stir, impregnated in 3 grams of Al
2o
3on carrier, drying at room temperature enters baking oven and dries 15 hours in 110 DEG C after 2 hours, 400 DEG C of roastings 4 hours, obtain Cu(43.9%)-Zn(14.6%)-Fe(2.3%)-Cr(1.4%)/Al
2o
3(per-cent relative to vehicle weight) catalyzer, numbering JQ-4.
[embodiment 4 ~ 6]
First reactor loads 0.37 gram of rhodium base catalyst Rh/SiO
2, the second reactor loads catalyzer prepared by 1.2 grams [embodiments 1 ~ 3].Wherein, the first reactor reaction temperature is 310 DEG C, and reaction pressure is 3.0MPa, and reaction volume air speed is 9000 hours
-1; Second reactor reaction temperature is 190 DEG C, and reaction pressure is 3.0MPa, and reaction volume air speed is 9000 hours
-1.Reaction product (full component) directly enters its composition of gas chromatographic analysis after insulation, and analytical results is in table 1.
[comparative example 2]
The performance of the catalyzer of [comparative example 1] is evaluated with [embodiment 4].Reaction product (full component) directly enters its composition of gas chromatographic analysis after insulation, and analytical results is in table 1.
[comparative example 3]
Synthetic gas is only through the first reactor, and reaction conditions is with [embodiment 4 ~ 6].Reaction product (full component) directly enters its composition of gas chromatographic analysis after insulation, and analytical results is in table 1.
Table 1
Claims (1)
1. a method for synthetic gas preparation of ethanol by hydrogenating, comprises the following steps: be dissolved in 103 milliliters of dehydrated alcohols together by 15 grams of cupric nitrates containing 3 crystal water, 5.99 grams of zinc nitrates containing 6 crystal water, 1.5 grams of iron nitrates containing 9 crystal water, 1 gram of chromium nitrate containing 9 crystal water; 9.56 grams of oxalic acid are dissolved in 55 milliliters of dehydrated alcohols, two kinds of ethanolic soln mixed precipitations under fast stirring, continue stirring 2 hours, suction filtration, filter cake drying at room temperature enters baking oven and dries 15 hours, 400 DEG C of roastings 4 hours in 110 DEG C after 2 hours, obtain 70.5%Cu-23.5%Zn-3.7%Fe-2.3%Cr catalyzer, compression molding, gets 20 ~ 40 orders stand-by, numbering JQ-3;
First reactor loads 0.37 gram of rhodium base catalyst Rh/SiO
2, the second reactor loads 1.2 grams of JQ-3 catalyzer.Wherein, the first reactor reaction temperature is 310 DEG C, and reaction pressure is 3.0MPa, and reaction volume air speed is 9000 hours
-1; Second reactor reaction temperature is 190 DEG C, and reaction pressure is 3.0MPa, and reaction volume air speed is 9000 hours
-1; The reaction product of full component directly enters its composition of gas chromatographic analysis after insulation, and the selectivity of analytical results display ethanol, propyl alcohol, ethyl acetate, butanols is respectively 53.8%, 1.8%, 0.3% and 0.8%, without acetaldehyde and acetic acid in product.
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| CN109126818B (en) * | 2018-08-17 | 2021-12-07 | 新奥科技发展有限公司 | Composite catalyst and preparation method thereof |
| CN115557829B (en) * | 2021-07-01 | 2024-08-13 | 高化学株式会社 | Method for co-producing methanol and ethanol from synthesis gas |
| CN113522296B (en) * | 2021-07-28 | 2022-09-16 | 太原理工大学 | CuZn catalyst for preparing ethanol by CO hydrogenation and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0297458A2 (en) * | 1987-07-02 | 1989-01-04 | Phillips Petroleum Company | Preparation of alcohols from synthesis gas |
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| JPS6259227A (en) * | 1985-09-09 | 1987-03-14 | Agency Of Ind Science & Technol | Production of ethanol |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0297458A2 (en) * | 1987-07-02 | 1989-01-04 | Phillips Petroleum Company | Preparation of alcohols from synthesis gas |
Non-Patent Citations (1)
| Title |
|---|
| 新型CuO/ ZnO催化剂的制备及其对醛加氢/ 醇脱氢反应的催化性能;赵乐平等;《石油化工》;20040320;第33卷(第3期);第209-211页 * |
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